Maltol tosylate and triflate possessing nonlinear optical properties [2]

Full text of DOI:10.1007/s10593-006-0267-z

Chemistry of Heterocyclic Compounds, Vol. 42, No. 11, 2006
MALTOL TOSYLATE AND TRIFLATE POSSESSING
NONLINEAR OPTICAL PROPERTIES
B. G. Sukhov, S. A. Mukha, I. A. Antipova, S. A. Medvedeva, Yu. A. Grigorieva,
A. I. Illarionov, F. Yu. Chuvashev, and B. A. Trofimov
Keywords: maltol, tosylate, triflate, second harmonic laser emission, non linear optical properties.
3-Hydroxy-2-methyl-4H-pyran-4-one (maltol) has a broad spectrum of practically useful properties [1-3]
and is a naturally occurring synthon [5, 6]. The subsequent functionalization of this γ-pyrone ring with highly
reactive groups is a current goal.
For the first time we have shown that tosyl chloride and trifluoromethanesulfonyl fluoride react with
sodium maltol (prepared from maltol and metallic sodium in absolute dioxane) to give good yields of the maltol
tosylate and triflate 1 or 2 respectively.
O
OSO2C6H4Me-4
O
O
O
O
a. ClSO2C6H4Me-4
b. FSO2CF3
Me
O
OH
Me
ONa
Me
Na
1
O
dioxane
–NaX
OSO2CF3
Me
O
2
X = F, Cl
With the use of the powder method [7] compounds 1, 2 generate a second harmonic emission
of a neodymium laser with an efficiency comparable with that for the classical nonlinear optical material lithium
iodate.
The chemical and nonlinear optical properties of the compounds prepared are being examined in detail.
1H NMR spectra were recorded on a Bruker DPX 400 (400 MHz) spectrometer using CDCl3 with
HMDS as internal standard. Mass spectra were recorded on a Hewlett-Packard HP 5971A instrument (EI,
70 eV). IR spectra were taken on a Specord IR-75 spectrophotometer in the range 4000-800 cm-1 in KBr and on
a Specord M 82 in the range 800-200 cm-1 using vaseline oil. Generation of the second harmonic was studied by
the powder method [7] with the action of neodymium laser irradiation on yttrium aluminium garnet (YAG) at a
_______
* Dedicated to Academician M. G. Voronkov on his 85th birthday.
__________________________________________________________________________________________
A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk 664033,
e-mail: sukhov@irioch.irk.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1725-1727,
November, 2006. Original article submitted September 14, 2006.
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0009-3122/06/4210-1368©2006 Springer Science+Business Media, Inc.

wavelength of 1064 nm, working with Q switch modulation. The power density of the exciting radiation was
about 108 watts/cm2. The spectrum of the second harmonic irradiation for the samples investigated was recorded
with an original laboratory optical spectrometer with a measurement error of less than 1 nm.
Sodium 2-methyl-4-oxo-4H-pyran-3-olate. Finely rolled metallic sodium (0.24 g, 10 mmol) was mixed
with absolute dioxane (50 ml). The mixture was refluxed with vigorous stirring under an argon atmosphere in a
flask fitted with reflux condenser until the metallic sodium had fully melted (20-30 min). Maltol (1.38 g, 11
mmol) was added to the suspension obtained and refluxed with constant stirring until hydrogen evolution had
ceased (about 3 h).
2-Methyl-4-oxo-4H-pyran-3-yl-4-methylphenylsulfonate (1). A solution of tosyl chloride (2.0 g,
10 mmol) in dioxane (15 ml) was added dropwise to the suspension of sodium maltol cooled to 13°C. The
mixture was stirred for 4-5 h at room temperature, diluted with water (1 : 1), and extracted with ether. The ether
extract was evaporated to dryness and the solid residue of maltol tosylate obtained was purified by
recrystallization from ethanol to give the product (2.1 g, 71.4%) with mp 110°C. IR spectrum, ν, cm-1: 1640
1
(C=O), 1615 and 1560 (C=C), 1580 (arom.), 1350 and 1160 (S=O). H NMR spectrum, δ, ppm (J, Hz): 7.97
(2H, d, J = 8.3, o-CH3C6H4SO2) and 7.35 (2H, d, J = 8.3, m-CH3C6H4SO2); 7.63 (1H, d, J = 5.8, H-5); 6.31 (1H,
d, J = 5.8, H-6); 2.440 (3H, s, CH3C6H4SO2); 2.438 (3H, s, CH3); 13C NMR spectrum, δ, ppm: 171.95 (C-4);
162.96 (C-2); 154.07 (C-6); 145.64 (CS); 138.76 (Carom-CH3); 133.42 (C-3); 129.63 (m-CH3C6H4SO2) and
128.77 (o-CH3C6H4SO2); 117.44 (C-5); 21.83 (CH3C6H4SO2); 16.10 (CH3). Found, %: C 55.73; H 4.19; S 11.28.
C13H12SO5. Calculated, %: C 55.71; H 4.26; S 11.30.
2-Methyl-4-oxo-4H-pyran-3-yltrifluoromethanesulfonate (2). Trifluoromethanesulfonyl fluoride
(1.58 g, 10 mmol) was passed through the sodium maltol solution in dioxane cooled to room temperature. The
mixture was stirred for 40-60 min, filtered, diluted with water (1 : 1), and extracted with ether. The ether extract
was evaporated to dryness to give the solid maltol triflate which was purified by sublimation at reduced pressure
(28°C). The yield of pure product was 1.96 g (72.6%) with mp 44°C. IR spectrum, ν, cm-1: 1657 (C=O), 1635
and 1570 (C=C), 1420 and 1125 (S=O). 1H NMR spectrum, δ, ppm (J, Hz): 7.73 (1H, d, J = 5.8, H-5); 6.48 (1H,
d, J = 5.8, H-6); 2.43 (3H, s, CH3). 13C NMR spectrum δ, ppm (J, Hz): 170.48 (C-4); 161.34 (C-2); 154.79
(C-6); 139.10 (C-3); 117.33 (C-5); 123.27-116.90 (dd, J = 320, CF3); 15.55 (CH3). Mass spectrum, m/z (Irel, %):
258 [M]+ (22), 189 [M-CF3]+ (1), 174 [M-CF3-CH3]+ (5), 125 [M-SO2CF3]+ (12), 109 [M-OSO2CF3]+ (1),
97 (26), 80 [OSO2]+ (8), 71 (6), 69 [CF3]+ (21), 54 (11), 43 (100). Found, %: C 32.64; H 2.36; F 22.31; S 12.52.
C7H5F3SO5. Calculated, %: C 32.56; H 1.94; F 22.09, S 12.40.
This work was supported by the Russian Fund for Basic Research (grants 05-03-97208 and
05-04-97269).
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